Process of producing ammonium nitrate and other fusible compounds



Aug. 17, 1937. ,1. D. CONVERSE ET AL 2,039,945

UCING AMMONII JM N'ITRATE AND OTHER FUSIBLE COMPOUNDS Filed Feb. 6, 1934 2 Sheets-Sheet 1 PROCESS OF PROD W17 7' i R V/IPOK fi/VHYDRO us Man s/v ammo/wan N/TRH r5 John D. Cbn vers Shin/g L Handfor/h INVENTORS Gem-gel Harris A TTORNE Y.

J. D. CONVERSE ET AL 2,089,945

PROCESS OF PRODUCING AMMONIUM NITRATE AND OTHER FUSIBLE COMPOUNDS Filed Feb. 6, 1934 2 Sheets-Sheet 2 Wafe) Vapor Jo'l z D. Converse Stanley Lhandfarzh INVENTORS ATTORNEY FY mm,

Patented Aug. 17, 1937 UNITED STATES PATENT. OFFICE PROCESS OF PRODUCING AMIMONIUM NI TRATE AND OTHER FUSIBLE COMPOUNDS John D. Converse, Shawinigan Falls, Quebec, Canada, Stanley L. Handforth, Gordon Heights, Del., and George J. Harris, Mount Royal, Quebec, Canada, nssignors to E. L du Pont de Nemours. & Company, -VVilmington, Del., a, corporation of Delaware Application February 6, 1934, Serial No. 709,968

19 Claims.

An object of our invention is a process for the production of substantially dry, molten chemical more satisfactorily than has been the case heretofore. which ammonium nitrate of much lower water content than is now practical is produced from aqueous solutions of this salt. A still further object is a process for producing fused ammonium nitrate, in which the evaporationof large amounts of ammonium nitrate solution in one body is unnecessary.- An additional object is not less than 98%.

For example, ammonium nitrate solutions, as ordinarily made by the neutralization of ammonia with nitric acid, usually contain from to 50% water. Such a solution is caused to flow A further object is such a process in l of two processes. By the first of these, the solusuch a process in which the hazards present in 10 tion is evaporated to a medium water content previous methods are avoided. Further objects and then cooled. The ammonium nitrate cryswill be disclosed as the invention is-more fully tallized in this way, is separated, and dried. The described hereinafter. recovered mother liquor is further evaporated We have found that the foregoing objects are and put through the same cycle. This procedure attained and the production of the substantially 15 is wasteful. of heat and also requires considerdry, molten compound desired is brought about able equipment. by causing the solution of said compound in a The second method consists in evaporating to volatilizable solvent to flow at a rapid rate, in n relatively low water content, for example, 2 the form of a thin layer or film over a heated to :10%., which is really a solution of water in surface, whereby theevaporation of thewater 20 molten ammonium nitrate. This molten mass present is substantially complete. While our is then cooled with agitation so as to obtain a process is applicable tovarious solid --chemica1 grained product. It is thus necessary to evapcompound-s, it is desirable that the material orate the remaining water from the resultant have'a fusion point without decomposition suf- 5 product at a lower temperature so as to obtain ficiently' low so that it will be in a molten conan essentially dry ammonium nitrate. The boildition, even after the removal of the greater ing point of fused ammonium nitrate with 10% part of the solvent. The invention has particwater is 147 C., while with 5% water, it is 169 ular application to the production of substan- C. .Hence, in order to evaporate to this low tially dry, ammonium nitrate from its aqueous 39 water content, it has been necessary to hold solutions. large quantities of molten ammonium nitrate at In the latter case, the solution of ammonium a high temperature for a considerable length of nitrate is passed at a high velocity, in the form time, and, even under these conditions, it is of a thin film, over a heated surface. In this practically impossible to evaporate such a mateway, since a minimum of material is exposed as rial to as low a water content. as is desired. to the necessary elevated temperature for only 5 Moreover at these temperatures ammonium nia very short time, the amount of decomposition trate decomposes, so that there is loss of valuais negligible. Also, under these conditions evapble material. In addition, ammonium nitrate oration is essentially a surface process instead so processed and containing only small amounts of a normal boiling. As a result, there is a mini- 40 of water will cause any organic material coming mum amount of spray which can be carried away 40 into contact with it to burn with almost explowith the water vapor and lost. We have also sive violence. found it advantageous when an extremely low There is, therefore, great danger under cerwater content is desired, to pass a rapid stream tain conditions of the whole mass of ammonium of hot inert gas, such as heated air, countercurnitrate exploding, which creates aserious hazard rent to the film flowing rapidly over the heated 45 when any large body of it is so treated. Fursurface. In this way, the water vapor is conthermore, when solutions containing as much tinuously removed and evaporation occurs at a as 5% moisture are cast or flaked, the high moistemperature substantially below the normal boilture content causes the productto become poring point. By such a process, a material is ob- 5 ous and to disintegrate on storage. tained having an ammonium nitrate content of down the inside of a vertical pipe in the form of a thin film, while steam at 150 lbs. pressure, that is with a temperature of 185 C., surrounds the outside of the tube. As a result, water evap- 5 crates from the rapidly flowing film and leaves the top of the tube, while the molten ammonium nitrate, containing 2 to water, is withdrawn from the bottom of the tube without the occurrence of any loss of material, due to decompo- 10 sition or to entrainment. If it is desired to remove still further amounts of water, this molten material may, with advantage, be passed through a second similar tube, up which a rapid current of heated inert gas, suchas air, is blown. If the initial concentration is high enough, the complete evaporation may be carried out in o stage by the use of a current of gas up through the tube. By this means,- it is possible to reduce the water content to even less than 0.5% and obtain a molten ammonium nitrate with a freezing point higher than 160 C. and at a temperature of about 180 C. This may be done with a heating medium no hotter than 185 C., even though it is practically impossible to reduce a fused ammonium nitrate to so low a water content by the ordinary evaporating means, heretofore available, since the boiling temperature is so high that there is almost complete decomposition. With the above procedure, when evaporating to extremely low water contents, there may be a slight volatilization of ammonium nitrate and some loss. that, by introducing even a trace of ammonia 5 gas into the'heated air, which is flowing countercurrent to the film of molten nitrate, this loss may be almost completely prevented, even when evaporating to as low a water content as 0.2%. Preferably the ammonia content of the air curfi rent should be not greater than 1%.

Ammonium nitrate is customarily produced on a commercial scale by the neutralization of aqueous nitric acid with ammonia either as a gas or in aqueous solution and the subsequent removal of the water from the solution by evaporation. The reaction of ammonia with nitric acid is exothermic and produces a large amount of heat. This heat of neutralization has been utilized in a number of recent processes for the preliminary concentration of the ammonium nitrate solution. It may also, if desired, be used for bringing about the volatilization of the water from the film of ammonium nitrate solution flowing over the heated surface. In this case the heated surface will be located concentrically within the neutralizer, preferably as an overflow pipe, and heated by the hot reacting products surrounding it. .In this event, we prefer to operate the reaction on the alkaline side, the excess ammonia being recovered and returned to the process.

An apparatus suitable for carrying out our invention is illustrated in the accompanying drawings, in which I is a vertical tube. surrounded'by a jacket 2. In communication with this tube chambers 3 and 4 are provided at the top and bottom respectively. Ammonium nitrate enters 3- through inlet pipe 5, rises in this chamber and. overflows into the top of pipe I through 7 slots 6. From these, which serve as distributors,

the solution flows in an even film down the inside of pipe I. Steam enters the outer jacket through inlet 1 and the condensate leaves by outlet pipe 8. Hot air, which enters the bot- 7 tom chamber 4 through pipe 9, is forced up Under such conditions, we have found through tube l countercurrent to the film of solution flowing down over the inner surface of the tube, and leaves the top chamber 3 by pipe l0, along with the water vapor driven off from the ammonium nitrate solution by its conum nitrate leaves chamber 4 through pipe H, for cooling and solidification in any form desired. As previously described, the complete optact with the hot surface. The molten ammoniwater. In other respects, this second stage is a duplicate ofthe first stage. Thus, I2 is a vertical tube with jacket l3, and chambers l4 and l5 at the top and bottom respectively. Ammonium nitrate enters the chamber is through pipe Ii and overflows into the pipe l2 through slots l6, passing in an 'even film down the inside of pipe i2. Steam enters the outer jacket through inlet I! and the condensate leaves by outlet pipe I8. Any suitable hot inert gas such as air is introduced into chamber l5 through pipe l9. Water vapor is driven ofi from the top of pipe l2. The-moltenammonium nitrate leaves chamber l5 through pipe 2! from which it passes to the chilled revolving roller 22 and-solidifies thereon, and from which it is readily removed in flaked anhydrous form.

While the evaporator described in the foregoing consists of a heated tube, it should be understood that other forms of apparatus may be employed. For example, a number of tubes may be placed in one heating jacket, or flat plates or sloping surfaces and the like may be used.

The fused ammonium nitrate, resulting from the process described heretofore, canbe solidified inany form desired. It may, for example, be poured into molds and solidified in cast forms,orit may be picked up on a chilled rotating roll and when cooled scraped off as flakes, or it may be sprayed to form granules. In any case, the low I water content will prevent either a caking or'a disintegration of the final solid. With the product of ammonium nitrate solutions, evaporated in the ordinary way and containing as much as 2% water, the high moisture content would cause the masses to become porous, to stick together,

or to disintegrate.

An advantage of the cast product over forms of ammonium nitrate previously available lies in its high apparent density, over 1.5, and practically equivalent to the absolute density. As a result of this high density, the material will not float in a molten ammonium nitrate bath, a property that makes this cast product especially valuable for some particular uses of ammonium nitrate, for example in the manufacture of nitrous oxide.

While we have described our invention for the production of a substantially dry product from a solution of said product in a volatilizable solvent in connection with ammonium nitrate particularly, it will be apparent that this process of concentrating a solution to obtain a dry product, by the passing of a film of such solution over' a heated surface is applicable with advantage to many other products, both inorganic and organic. Among .the inorganic compounds, to the prepara-.- tion of which the process is applicable, may be cited ammonium acetate, sodium, acetate (NB-CaHzOz-3 H20), and sodium sulfite. Similarly the method may be applied to organiccompounds, for example to the evaporation of urea 5 andsugar solutions, the concentration of tartaric acid preliminary to crystallization, and in many other cases. It is apparent that our invention is equally applicable to processes in which either water or other volatilizable solvents are emto ployed.

We intend, therefore, to be limited only as indicated in the following patent claims:

Weclaim: l. The process of producing a substantially dry 15 molten compound which has a tendency to de-' compose when maintained above its melting point, which process comprises causing a solution containing said compound and a volatile fluid to flow in the form of a continuously moving-film 30 over a surface maintained at a temperature above the melting point of the compound in the anhydrous state and maintaining the rate of flow sufilcientiy rapid and the time ofcontact of the film with the heated surface suficiently short 35 to substantially avoid decomposition of the compound, but sufficiently long to substantially dehydrate said compound. 7

2. The process of producing a substantially dry molten compound melting at a temperature at- 30 tainable with superheated steam, which comprises causing a solution containing said compound and water to flow in the form of a continuously moving film over a surface maintained at a temperature above the melting point of the 35 compound in the anhydrous state and maintalning the rate of now suificiently rapid andthe time of contact of the film with the heated surface sufficiently short to substantially avoid decomposition of the compound, but sufficiently iil'long to substantially dehydrate said compound.

3. The process of producing a substantially dry molten compound which has a tendency to decompose when maintained above its melting point, which process comprises causing a solution con-- 45 taining said compound and a volatile fluid to flow in the form of a continuously moving film over a heated surface countercurrent to a stream of heated inert gas while maintaining said surface at a temperature above the melting point of 50 the compound in the anhydrous state and maintaining the rate of flow sufiiciently rapid and the contact of the film with the heated surface sufilciently short to avoid decompositionof the compound, but sumciently long to substantially 55 dehydrate said compound.

4. The process of producing substantially dry ammonium nitrate in fused form which comprises causing. an. aqueous solution of the ammonium nitrate to flow in the form of a continuously mov- 60 mg film over a heated surface maintained at a temperature above the melting point of the ammonium nitrate in the anhydrous state and maintaining the rate of flow sufiiciently rapid and the time of contact of the him with the heated sur- 65 face sumciently short to substantially avoid decomposition of the ammonium nitrate while removing the water therefrom.

5. The process of producing molten ammonium nitrate of relatively low water content which 70 comprises causing a concentrated aqueous solution of the ammonium nitrate to flow in the form of a continuously moving film over a surface maintained at a temperature sumciently above the melting point of substantially anhydrous am- 75 monium nitrate to remove by volatilization a substantial part of the waterv present, maintaining the rate of flow sufliciently rapid and the time of contact of the film with the heated surface sumciently short to substantially avoid decomposition of the compound and maintaining'the molten ammonium nitrate in. substantially anhydrous form as it leaves the heated surface. 5

6. The process of producing ammonium nitrate which comprises causing a concentrated aqueous solution of the ammonium nitrate to flow in the form of a continuously moving film over a heated surface maintained at a temperature sufflciently above the melting point of substantially anlwdrous ammonium nitrate, whereby to remove sufficlent of the water present to obtain a final molten product having an ammonium nitrate content of not less than 98%, and maintaining the ammonium nitrate in molten form as it leaves the heated surface. a

7. The process of producing molten ammonium nitrate which comprises causing a concentrated solution of ammonium nitrate to' flow in the form of a continuously moving film over a heated surface maintained at a temperature above the melting point of the salt in the anhydrous state and maintaining the rate of flow sulficiently rapid and the time of contact of the film with the, heated surface sufiiciently short to sub-' stantially avoid decomposition of the ammonium nitrate but sufficiently long to remove by volatilization the greater part of the water present, and flowing the molten ammonium nitrate from the heated surface.

8. The process of producing ammonium nitrate of relatively low water content which comprises causing an aqueous solution of the ammonium nitrate to flow in the form of a continuously moving film over a heated surface maintained at a temperature above the melting point of substantially anhydrous ammonium nitrate, countercurrent to a stream of inert gas and recovering molten ammonium'nitrate substantiallyfree from water as it leaves the heated surface.

9. The process of producing ammonium nitrate which comprises causing an aqueous ammonium nitrate solution to flow in the form of a continuously moving film over a heated surface maintained at a temperature above the melting point of substantially anhydrous ammonium nitrate, countercurrent to a stream of hot inert gas, removing sumcient of the water present to obtain a final product having an ammonium nitrate content of not less than 98% and recovering the ammonium nitrate in molten form as it leaves the heated surface.

10. The process of producing ammonium nitrate of relatively low water content which comprises causing a concentrated aqueous solution of ammonium nitrate to flow in the form of a continuously moving film over a surface maintained at a temperature above the melting point of substantially anhydrous ammonium nitrate coun tercurrent to a-stream of hot inert gases to eifect the removal of a substantial part of the water present, and maintaining a small ammonia content in said gases.

11. The process of producing ammonium nitrate of relatively low water content which comprises causing an aqueous solution of the ammonium nitrate to flow in the form of a continuously moving film over a heated surface for the partial evaporation of the water present, and then passing the resulting solution, in the form of a film, at a rapid rate over a second heated surface maintained at a temperature above the melting point of substantially anhydrous ammonium ni: trate, countercurrent to a stream of heated inert gas to remove a further portion of the water content.

5 12. The process according to claim 11 in which;

the form of a film over a heatedsurface main- 1 tained at a temperature above the melting point of substantially anhydrous ammonium nitrate,

countercurrent to a stream of hot inert gas to 15 evaporate a substantial part of the water present, flowing the molten ammonium nitrate away from the surface and converting the resulting product into a predetermined form and cooling it to a solid in such form.

14. The process according to claim 13 in which the molten ammonium nitrate flows into a mold and is solidified in predetermined cast form.'

15. The process according to claim 13 in which the molten ammonium nitrate is chilled to solidg5 ification on the surface of a revolving roll and the solid film is scraped off in the form of a flaked product. y

16. A process for producing substantially dry ammonium nitrate in fused form, which com- 30 prises rapidly ,fiowing a concentrated aqueous solution of said ammonium nitrate, in the form of a'film, over a surface heated to a temperature above the melting point of substantially anhydrous ammonium nitrate, and of suiiicient 35 length to provide for removal of substantially all water from said ammonium nitrate and the fusion under heat of the ammonium nitrate, and flowing the fused ammonium nitrate from said surface in molten and substantially anhydrous 40 form 17. The process of producing a substantially solvent-free molten compound, which process comprises causing a solution containing a volatile solvent and a substantially non-volatile com- 45 pound which melts in the purestate below'its' decomposition temperature, to flow in the form of a continuously moving film over a surface maintained at a temperature above the melting point of said compound in the solvent-free state, 50 but below the decomposition temperature of said face in a compound, maintaining the rate of flow sumciently rapid,- and the time of contact of the film with the heated surface sufliciently short to substantially avoid decomposition of said compound, but sufllciently long to substantially completely remove said volatile solvent from said compound, andcausing the substantially solvent-free compound to flow from said heated surface in a molten condition.

18. The process of producing a substantially anhydrous molten compound which comprises causing an aqueous solution containing a substantially non-volatile compound which melts in the anhydrous state below its decomposition temperature, to flow in the form ofa continuously moving film over a surface maintained at a temperature above the melting point of said compound in the anhydrous state, but below its decomposition temperature, maintaining the rate of, fiow sufliciently rapid and the time of contact of the film with the heated surface sufllciently short to substantially avoid decomposition of said compound, but sufliciently long to substantially dehydrate said compound, and causing the substantially'anhydrous compound to flow from said heated surface in a molten condition.

19. The process'of producing a substantially anhydrous molten compound, which process com- 7 prises causing an aqueous solution of a substantially non-volatile compound which melts in the anhydrous state below its decomposition temperature, to fiow in the form of a continuously moving film over a surface maintained at a temperature above the melting point of said compound in the anhydrous state, but below the decomposition temperature thereof, countercurrent to a stream of hot inert gas, maintaining the rate of flow substantially rapid and the time of contact of the film with the'heated surface sufliciently short to substantially avoid decomposition of said compound, but sufficiently long to substantially dehydrate said compound, and causing the compound to flow from said heated surmolten, substantially anhydrous condition.

JOHN D. CONVERSE. STANLEY L. HANDFOR'I'I-L' GEORGE J. HARRIS. 

